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Class notes 15 and 16 from Rogers

by: Carlos David Fuentes

Class notes 15 and 16 from Rogers CHEM 2322

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Carlos David Fuentes

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The page 16-12 is added at the end of the file since I skipped it by accident. You can check these notes to compare them with yours.
Organic Chemistry 202
Frank Foss
Organic Chemistry
75 ?




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This 32 page Bundle was uploaded by Carlos David Fuentes on Saturday February 6, 2016. The Bundle belongs to CHEM 2322 at University of Texas at Arlington taught by Frank Foss in Winter 2016. Since its upload, it has received 66 views. For similar materials see Organic Chemistry 202 in Chemistry at University of Texas at Arlington.

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Date Created: 02/06/16
Tan zJ {0-15 t5-1 Chapter15. lnfrarSp*troscopyand MassSpectrametry lntroductitolnfrareSpectrocopy Lr ErectromagneticRaAia,!r*o,,tueg{h*lr-rv.iI,*ugltpac,oq*Wspeedor I*g#;[rx oceeifq{pnglrhro-^d ;-r*lir'i,,rU, tWUteknSlL, tt\,pnl v 'tnrP"qr*.y ) r#, 1W= l_* =-l 8J E Lnn,5y pl.r*o+[- P.htr "[q n 0funct's (r,(2$il0-rfUs c"ls{qd, csperd Inrg S^d "A C=-2,"918x_]0 Fundamentarequations: \V. C,ro tr\ + L'\.r u',E\r ,.' hC ,to En.,j \ You must kthe relative ordering of tof the electromagnetic spectrum: E,V Y no,,. Xr.1$ rrv 6ffi,0rr rR lmportant: ithe wavelrange visible,,rn,,y;An, E00- The way the electromagnetic rwith molecules depenenergy: its uv,vrshr:f rnCh 15 *MR Ch 16 TY,xf lrlr--+ D Z l( L/ ^[Firsborr{ k,y*"toe*konquL co{ug"{a*lortlA oPprufocs lmportantEachoftheseenergyevelis andinorderoa molecultogofrom ste lower , Jla LY L*\wu^ llv U^o*/,k hrtrareSpectroscopy 1. Units used lR Spectroscopy: waverengthilfi. Wir7lrnJgr5, 7A-L -lp,r" Frequency:*rrgr1,.rqlr6/'or rrcof [[= *wua . cnl p,acolLn" C,rn-l C,t/) 2. When lRlightabsorbeby amoleculthe molecuchangesits r,rf[rodt'oas Thereare two tofmotecutavibrations:gl.t+0hP,?q. hen1/lrlq^ ^na Examples: o' p{..}shrq wb.e^lten H-cr > pg What happens to the cof masofH-Ct?rernql46 VC*AAyd O=C=O -- 0,t---O - O=C=!t- + -) k?"t ThereforCO2 has3vibratiomodes. EthanolCH3CH2OH)has 21possibvibrationsheoreticabut most are for C-H vibrations. 3. lmpoftancofPolarity Notalloleculavibrations absoradiation. Anon.polarbonddoes not absorb lR r:adiation. Examples: i'l rL '\" -rku .{r,lo \-- ".rtr 11' \ tL/tb+ fR ustw, G, Zf tfr)Sp.polbonddoesabsorbh.o,"oon. Exampte: p- Co'6sy/ G*uq o'.4 slrong,ota.p rho"pi*o.r W.y pohr ru J?ZA 'J o^-r 15-3 Only unsymmetrically substituted bonds have dipolareinfareactive. o" Exampres: rRActive:q lermfnal olkrlneeff&clae=ffiJl? No*RActive:,o a Agne CH;r{-frUtnq'ltve 4. Thefrequency astretching vibration to:related 1)Ihe ui*r*+hs[lfu,fund ,tTlwhaEs+r EI llw q{hched q.f...N lngenerathe lighthe atoms,n" hfglre, therequencabsorbed. lngenerathestrongerhebond,tne hfghgr the trequenabsorbed. lnterpetinlRSpectra 1. Knowthegeneralregiointhe lspectrum.Memorizthese numbers.) Bhob hrnJo+o# ;*rptbqd eldotes d*,61ebad shtdlr.0srr6,,bond sl"ahta C*to+otr.l I 'L.: V (.=(, t1(050 F& C-C C=fu C=A/ C-lV 0-H l\trl+ C=O a-o ^,-1*20 C-x &r#q urL,qllon 'bposrtk o r?g?&n" w /' lf+.rohrq ;Lttgerp,9wl ort w&q{*,4s4 i t{o0oc,.< 2b00 on 7N0w-a f,509--: W0r-ra 2. Know the appearance of an lR spectrum: ldCI7. A*il, ! l"tsn*l- hqcg ff*&Detectvr fu*t 0fo lfuarplet,A",Js 15-4 Loofor distinctive absorption(Menrothese numbers.) 1) 5000 cn{ n'd*f{* l.Aca6hfol }000 cra-r" Legso-sosol Cbptl-ps 'fitraflJ& W tl B00o *n-.' CGp+ H AH C50od-3ro&} t,)300 o# C(*p)- U 50@ gr'1--l 1h/,nhtllnrn4 2)J}ZO cm'1 o Lruya-J40, -w (r- tjeroh,06- kehqs ltloqro Es+u 'vJYLAcrt-3 ryflj0ur'r-r .uJ*q0 ?,k1< onoslo,tl8,t* ghq^p "r6t o 0 -\,/' -\^oA c*r4'ugaklarto &qrgn[d ,lde\ydo Eek, * J6&A cnt a,J a,JlJ0d 106eanJ c.,nr all4yJru,tbu,tdponsu/rt ?q braqdq&eo.pEorg exct'.hs+ )tu 6r" 4 frorb,vqd 3000ch-l nhd*, rsnaa qfcrl,*twg.-b6oo uh=l +) Cn,bs*,1jlrcq6'S, houe lots,e l+hrrd;;' ' 0*H-9 cvi(- ') \o- )c-clr.e tt*a/ ,& qcek" q.fJ &** wavelenglh(pm) lm2.5 3 4,5 5 5.5 6 6.5 7 r01ilz 1416 aehtt u 80 -\r/\/\r/ G' '560 <3000 st' c-# o En J3CI@,/Jry*S [)40 kJ Nnrth,ll-elhyt q z0 {*?rir 0 6qu 4ffi0 3500 30$0 2500 2000 180$ 1600 r4,o rz(n loff) ----)-) wrvcnumbdr fcm*l) - fingerprire-{iott wavelength(pm) ,*f.5 4.5 5 5.5 6 6.s 7 I l0 1112 t4 16 hexonu u.}*ot- 9I ./\r/\-r/ H ,rl ta <t00CI sf C^H Ed ru -;I 130a {) /:{ts B. v w"hy !-<\ltl*:,u*stq iL 4000 3500 3000 2500 2000 1800 1600 t400 r+,nvenumbe(cm-t; 15-6 'ZG wavelength(pm) J**y 2015 ,1 100r 4.5 5 5.5 6 6.5 ? l0 il12 14 t6 !-ht l.- xe,ts o 801 E ts I nt 601. Lcrys 'rr,unt s, y -rf (), rl) O. ,rr I 4000 3500 3000 2500 2000 1800 1600 1400 r200 1000 800 600 waverumber (cm-t1 ' wavelengt(pm) 2.5 r00r 4.5 5 5.5 6 6.5 7 I 10 lt12 1416 F rcler, CPS-{- ol 801- (nI L EI 601- ^va,r^- Ut il6l7ot)lje,.r L, b0 ZO c*-r ID -rf (j 882 c- lt/ E. <3e00 8p3 C-ll *1(o50c;1 h*ofl :L f-n 3500 3000 2500 zooo rSoo v-u reooi+oo 1000 800 600 wrvelengrh{pm) ?.s 3 3.5 4 4.5 5 5,5 6 6.5 7 I l0 1il2 t4 16 rmr <3000 Gtui'1C-l) *ol- zSza -c6-f./ () L r$ ?1zA - C=& E uo tr L- Q fu^qhru aikyne En {) on l- J--@cryno 0) L o" *f =_ h'4. oL 4tso 3000 ?500 2000 1800 16r)0 t400 1200 wavenumbcr (on-l) 15-7 wflvelBngthm) ,*f.5 4 4.55 5.5 6 6.s7 t0 1il2 t4 16 <aa00 sF o *1. RI Q-'o\ne :i *l rA -=1 l kl, {, *f M 3300 cr.t to o, ,:L 40fl) 3500 3{X}0 2500 2000 1800 1600 1400 1200 1000 800 600 w'.rvc$umbeim*11 wuvelengthpm) 2.5 4.5 5 5.5 6 6.5 7 I 9lOlll2 l4 16 lmr Atku(, ^60s0 "80 >= Jr 'E '/r\ 2 60 L ,"J6fl *" 4tl () a. 20 0L* 4il00 35m 30rm 25fi) 2000 tB0r) 1600 1400 120{)r000 wavenumber{cm-t) 2.5 3.5 4 4.5 5 J.s 6 6.5 7 I 910ill? t4t6 '*r o l)(.ono (,*n t- d 4,-[ TJ tl)nf 0, 6. ,:L 4000 3{100 2500 2000 1800 t6{,0 1400 1200 1000 wavenumber(cm-li 15-8 wtrYclcngthml 100.s 4.s 5 5.5 6 6.5 7 t0 lr12 14t6 sps G/C z&aa ())0 sp &/rl zt[a ftl ulky4o IJ60 ^le,nn,nol 6 3p'&,+/ *3JilA TJ CI40 zl(a Lzc H) E} 20 i;ffi} Be4zens nPs 0 4000 2500 2000 1800 1600 1400 1200 1000 800 6m wavenumber(cm-t1 wavelength{;rrn) 1{ 4 4.s 5 5.5 6 6.s 9 r0 1il2 14 16 r00 4, o/er1,*1 80 {J -5500 cr-J (!t Eh% aqd bn$) O-trr!, EI60 d J-L*tqnat 6)40 .J CH6CA,-CI+LCnfOt N o.20 ?500c.a 0 [6ruot/ 4000 3500 3000 250u 2000 1800 t600 1400 t200 1000 800 600 wavenumber (cm-t; wuvelengt(pm) 2.5 4J 5 5.5 6 "l l00r 6.5 l0IIl2 14t6 q la a,nlaa q) roI u dryaglun?na lj Ut -[ c["chct+; E f:ro_*l,cls {J *l- td) t, b*alrnodwh Or,rt Qi'*5369 o1la0 0",4 /rA_ ,I 4000 3500 2s00 2000 ls00 t600 1400 wnvenumber (cm..11 15-9 wsvelength(pm) 2.5 4.5 5.5 100 r 6 6,5 7 10 I1t2 14 16 ' (z@ao 80F ega GN qr L JYJZ C=g {{ &p aI *1. tr T-bept GI r *ru (} *[ t) R kx,. iL 4000 3500 3000 2500 zuoo lgoo 1600 r+ffi0 rvnvenunrbe(cm=l; wavelength(pm) 2.5 100 r 4 4.5 5 5.5 6 6.5 ? I I I0 lt12 l4t6 ln wihhyda o,80 d b&no,pnJyL 'E aa60 d -,--zeVtt (J,, efi$,4?0 OJ 20 ()1 .-__,i 4000 3500 30H] 2s0(l 200u t800 !6rru 1400 1200 1000 800 600 wavenurlhcr(cur-l) wavelengrhpnr) 2.5 l0t) 4.5 5 5.5 6 6.5 7 t6 fieaqart6q6gl iJ 80 ffrrr1P q, *'ou !, 60 I hd zs004Saa 40 SJ () r 20 0 \-/ 4000 3500 3000 2500 2$00 1800 t600 1400 1200 t{m0 800 6m wavenumber(cm-I) 15-10 w&velength([m) 2.s 4.5 5 5.5 6 6.5 7 l0lrr2 1416 '*r GlilrLr,ra n}80 [- ff*AvzPt tll ,-?* tl,rf GI r 27: s 6 4()l- z@20 (J L o. 201- .,L 4000 3500 3000 2500 2000 t800 1600 1400 1300 1000 800 600 wilYenumbercm-t; uavelengt(pm) 100[ 4:55 s.5 6 6.5 ? 8 9I0tn2 1416 b Jo ang,to (}80I. Gt (-ff$"'t'ePrrcesl ,rl q -l TJ \r6u I) *f <) l)-t# hsqt g. :L 3500 3000 2500 ?M rsoo r600Gd wavsnumber(crn-l) lllassSpectrometry 1. Mass spectrometry can be usedetermine the of a substance. 2. ln this technia sampleis UOpOnflerd and then with a stream of el-,1"^.1 f.aW%4 4. hgrrr*o{tOO occurs,wtrich can ofienideother structurat information 15-1 s. The l.rl093 C\qr5€/ ratisymbotizeabq/L is measured. '-r The NassSpet:trum \_-/' prnk Utryee*pa( Lloonqlr{oJ JWy, w)*" ,lr'4+1 prk Gonsider the mass soeofmethane: . ...j.reletive o80 mlz abtmdance 14 1 3.36 E60 13 8.09 t 14 t6.10 .lo 15 85.90 E20 i; roo.oo(ba$epskrrulec,llor pl.rtkfogc t7 ','.'t7 hoflr^ fo nluok- $p l0 trt+-.t1ii"l. brss prqk m/z Formatiof the molecular ion, CS4%[CI6J*.f s- LY)*'= J6, ro ll'rc uao,olw 4lre&eee Peo\ ' (M+t)*'pearnisisdueto4hepnSUCea!- lSg 1,1/y ,( no{,.,*ily oao"r&SC fs !6 r' tt 'iI rrtt 1'C 98,?/, :r-/ o,, J.l,7. s( Ma hesyh{oL LMJ+, rr LilAf otherpeaksconespond--B*^*{a lu-" congzruryos[ o-, Ctrq-\s7, fc l1,lr' <ffiJ#u. \.c}++ +511, lq}'+qlf Whichfraomenare most likelv to form? Thrse ;-.€ hW,'?u#*+*6/o *lt * qnJ "q&ols Carbocation stability order: 7') To,nilylrbn"ybo> 1') lutru* Free radstability order: uilyrobenrylr; 3')r";f ) tula)Vtnvl 100 80 60 40 20 0 10 20 40 60 80 10 m/z* Consider the mass spof hexane, saboveAccount for these m/z BTzf\tj peq"k peak ,1u-l'J $f, aozf{+ ^.Ldo.lonr o{uo{, W] . louoFnellr/6Nop(CHsl 6t% a{ t'4+ k]*--,r.rr*f I^ ' ,Clr eH:r P' 1"{-9f, 29 lrror"hl (cllrctlzl los: ptpvt"rf --+ t ,/\/ iw, .tl'tt ' ^k\7qil-+6 ?s 9a Why i57the baseak? Ard,{e euq k",,\L[eqoAu -l"gq{pr,CInJq J" ^/r.o/ 15-13 Doubl*tacusrhgmass spectrometryr,"l"o"rrht6A rtS-.r#p*fErgsflClronne+ry iable to determinevatues,o I derl^oi OlnCaS Abundarre 1H 100 1.m783 C0" J2 +16 zzSJ ,H 0.015 201410 13C 100 120m0 Mu= Lxlz*qr:g, lTN 1100 14.0815 F( ,5N 0.38 15.0001 160 100 15.9949 q) 1&O 0.04 15.9991, NL Mtu,e*il xscl 0100 34.%89 37Cl 32.5 36.%59 DBr 100 78.91&3 81Br 98 80.9163 Example: How can high resolution mass spectrometry distinguish between CO,CHr=91.1and N2? c0 w.JL0o00 *lt.?r{J. \l,lylq *1 C,Jh 7n, 7'{72.i//i00 xJ'(9CI7. zbNS$ furW,zuJ{,,t(lfi =Lo,aoL2 The NitrogeRule: nn Odd moteculaweight indica"ns edd number of nitroatoms. P))(4 a{ ($lng}n qlo.z9 An m ttclalarweishtindicael*[\u hoqise^,y Uar En Aka'qanh<, at The(M+1)" Peak The relative hofthe(M+t;"'peacan assiindeterminithemoleculaformula. Ex: (M).'?68, relaheight=100% (basepeak) .r,111,-a6e,relatiheish= o.t* [xjrZ,e8 4i% l,, eb UW,n, Ml{ .-z la) i-a loo 2_b Q{o 1r4+stw % PsJJl, o[ 1L(., -T J.f,93! ,q.{co}oo C,,l+,,CI Ex: (M)-'q96, relaheight=19.0o/ootbasepeak) (M+1).'a97, relative =eighto/o Cvxsz,rr$l Pnrcrrlq*zeafe ndq9.ouh'/l\o.Lqsopuk $o Ar.s["qor,'\qf?]o 14+ /-lr I M*.J /* lz*1, st l-szl i,S[ ,l.,ggz 13 W'. ^4 W.hzx* 15-14 The(tt+z)Peak Chlorine's two isotopes: 'r'U |, W+U W"k{rtqflPs ,-I +lrehef,.o(l t4t, J@/, >L,y, 'nct (rntot'l.n ss0ll Brominetuoisotopes: WB. saal "0,W#21 prak +{rua d*}q h{lb go,h,4io, {ho.M+ prk gby, ErB. tadine ra f ro pwnf, [ou r,uusuqllw ko gry*ertco( iloqlq w f+4-12y. "T r.effl;y.4dhlh6 {rn se Q J2F tratirn1 1" Iw al f *ample: Whicofthese fmass specindicate thesenof chlorbromine,dinor nitrogen? t00 1.56 80 - f? () -- E'1,,'$qe, Eoo +r Eat -rl Labsq d 20 -N 0 2D 50 6t)70 80 90 t00 ll0120 130140 t50160 qusE, rnlz -Jrt i00 a 166 --I+ r 80 60 a? 'fl z*tz 4A 3u 20 c/tclr2r 0 i0 20 30 40 50 60 70 80--a0 120r30 140 ls) 15-15 t00 80 90 -bs a ,J60 B 6i 4b lxll=4$ !d40 c I 20 0 Qrtyct t0 20 30 40 s0 60 '10 80 t4+1ll0 120 130lzto150 160 mlz ooI qorbe. t'- add *l fndru*reqn eddfl alN o (d) 'd,ol- : 3 +i CJ t00 --xtr++ i ;1, .-1-..*r5.'-.-- l, . ol0 r00 tt0 130 t40t50 t60 Degrees of Unsaturation/ Hydrogen Deficiency lndex UMu+Z ethane* tl, Crf,lo frqg'l{e naxlmom nwbrrl I}s pqd/e urflfs0,6e?s. H-i- +- u /. ol,led 'bqi*^il*J ift rn 1 ethyleneoetfi:ne) CrW hw z W hyt*gnsl4as J, dqrse op L,=c. j, calld uu4gr#.rnqftd,'J tl,,sq+1,"E1rt[rc];0,,t- u' 'lJ J 2_l<rr, l]) "unsaturated" 4 *lrr*lo u4JI11 *^* Tt bo'rts Becauseofitsdoubrebonds,anarkn^s Peult kyl*guS thantheconespondingarkane. ff,'i::; M Eqlu.q{rd Crll.o o 9",,eu/z\ N1E, y .\n 15'16 'ttlu{u,< ta}.Q^ l,t rsg J$Po4 C.ilro ,u,{$,ewy tr6alxt Nrcn qro 2 {r*, N3 CrMa ACI I Nts and .1 ftboot lrno ,-, Y uen{rrqlPo, tmpottanEach degreeunsaturatcorespon Z hrdrOqA*q Asn --_------=- fewerthan thosasaturated alkane. lmportanForeach degreeunsaturataomolecuwilleithhava n9g or, {E brnd Example:C6H1s Compare to saturatalkane:QHtq Degreeofunsaturation, o'uh"wfuo nrngs or lnt6.i"a: fiba4d w Z lt,bandS Example:Draw the structure of naphthalenetheoleculaformula witcounting hydrcgens. c,,llo &tu*led Usil22l ft; }o o&eufu.qk* ^\fi a Todeterminthe degreofnsaturat,follow these two steps: 1)Determine the footrn" CO.r*8,p.dP4\ hud{AUrhen -----r---- thatsthe hydrocarbonanequivalent numotrde$rya1 SL OtnnOl$rqlpr, .Forharosen",CdJ#X l" #14 slbcllzcl C[ra4o N .Foroxysen,NgnW 0 e|p"{,}tlL .Fornitrogen,$u!*hIc# N ** #ld 2)Comparethatormulathe F,q+,J.qJ.J olkgqu (cnHzn*z) 15'17 Examptes: 1 ceHs ww l, cuil.4 \--l @* "'!- -Q -r' $ 8'3' @ r 2 c7H7No2 eol46 sanpnal" c*ilta 9A' A:ffiHX r*ffi q-e 3 csH2c)cil*l*gQ{rg +h ,t,1 -__rl 4.The molecular formula of iC16H13N2Calculate the degreeithis compound.n GnHr.@*) Z4-12"?Z (*r&.u) JJ'uasqf Qnl+r, F - 5.A compound ofCraHrcontainsrinHowmany molar egofhydrodoesabsoiall \--l "[;*i,r';""Ior,ations are double bonds? /\,/ c"H*B,^+ Eq]'tCnlso Tr- 6qU CC.lno Zr,A- +ZlJzA* "?, ds$ ursoJr;+f; ^,1 , nrols ,'r 6 ro6o,rdS 6.Compound A has thCroHOn catalytic hydrogenatiireawith 2 molar eofivalents H2.Howanyrings does compound A have? Cro&l=) Crolt, .'oC-a,"pAanhqd216boodS qr'ilnP,5, @ c*u,q+" 7.How madegrees of unsaturation does benzene have? t/'drgrteo O *{ ansqlu*,{yaCrHn '16-1 Chap&r 16. Nuclear Magnetic Resonance gpectroscopy R*cathe fourntunumberf-;;@qwot-t")\wb4dttatte ;;"{;;;,i, hp# + lL + Protoand neutralsoave \ppn'++ When one of subatomicrticles "iteneraaesll1.nqnrktk )d A collection oin the absoan external Acollecofonotoinan external magnetic field: magnetfiel*16r"rdrfarq{fon (twspin states) tu { w.*, 1# an qppW Q Q s 6c exknal 0 i 6d '**'$ { a ,nqrntht 0 { or freta o r *n*0 13 'F\ The difference in energy bspin states dupon:s tt'fiveWA a{-Fheopplerdg*eka h"ld zl eq$rolnai Tht drrl,ar& aY ke pr"la4 V f.rcnrqrag r/ qk *twsW * The nE conesponds to nsl,qnt[r"lrrld A p^$s*U, hury ol- ot nlcaWq,hq ,qdp"[90, '--NdA Wheir apnrtonina stronextemal magneticfielahorbs f,qdp [9OO uslpn^ causingitto changspin srates, f-|/*P! ,theproronissaid tbe Fn fV*O$lnCg, with the rf radiation absorbed. rhe principrbehindNrun: qn extena! Rquf Ad h [ppl, nq4(l.rc k"ld Aqt d$trn?ne lho UrgU kp*,-Akp'qp*kr, $s-v Some typical numbers: \-/' Aoolied maqnetic field Frequency of electromaqnetic radiation reforaedoin-flip' Note: Alofthese frequencieareinthe range. So how does NMR providuseful informatisn? Beftuaav= Where Beffacliw = Brot = 16-3 PrinciplAn etectrctouwilt'b{fl*ld'c,nr,JL,{* \-/ Example: i elo,rd *AkkGdrlF*'isn L 6;0M,u C (o -S .i.d,,Aor.rul, $'tr&Utlrc& doz5oo|qbeo& il; lCCo( na ,f09er $r+qOnf rc50'sn1g Br'-1, Du,1,1l99ZgT rhestrongerapptiedntenpz,*qde6 rqrrl4o S,fife]dfns lmportantThe nucleus ofatom winet spin will exhibit thThus, NMR can be used with any nucleus containiQ4 *dd # of-p,ulorJor u4 odd # a( nr,rl,oos Ifd ilc {p roexample: ry prE{so The magnetfield experiebythnucleuisaffected Urn .lrrl**i uvkonne,tLoA lhL q*kus, Tl't$ *e+.uneii'yi+slsao C{t T}rrup^for 6 dqtttretdel affi-@ Ct NNIR 'H Specfros copy Thesetermsareusedinterchangeablv:', a,rl ltyr)*grn",hrdrus *[. Wq{.o,rr A1H NMn spectrum providesfour kindsofinformation: ry,,qitoLaq'rals: ''T[l. trnoJprq]Eh*^on, krros r( pn*/sns q<?q q_ntqlw,k, , Th,-poe?lf,ona( Nrusr$rt ",,Th';t,Cltunttd}lhtA'..t'0o, +al6 usq6.,^tUroek fo'fuottv$cavr^{ aP 14sp"th+ ' rr z.TTv-jnfao*lyat llw sr3ryil., 4otb lht urlxitwn$rt$ otp*lou *\eq.A ,kad Lt {r2orl+.r;arysa,$*qrafh the P*4 - qfu^${fup^foa* Vloff*o _a(kswrJ, nulhplreil1&llsm oradfaan]afu,ns, The n{^l n-/r, 1. PrinciplProtonin ditrerent environments arc nonequivatandabsoreneryatdifferent frequencies. Therefore, the number of signalmany kinds oftoarenamolecule. Examples: Determine theofonequivalenttons inthe following compounds. CHe-CHz-Cl 2 qb F-Cab-CHz-Br Z Br-CHz-CHz-BrI qqi q CHg-CHz-CHz-CHO q. bt,d 2. Thechemicshiftaluindicatteetectronic envirafmtherotons(Tabl16.2) 6 type ofoton proton 6 type tf *0"9 [-CS rtehql z-q X-?- ! utt'yt hoirao N!2 )ry. I ^uWrt* J^) rg q/co4ql *J,Y ne{hyne T= i-$ .,.rf ullyhc $,s- 66 )=(,, vNn4p /\-..y ArZS -c=G- tgolkynu! 616-8.0 aron^bo Ctru alJ,.yro ^r2S Ot$ b^.ytr" ^{0 r,&lr co"baxYP qcrJ -J0_ry Q- Lr,* ]' t t 1&5 Table16.1 FunctionGroup Effecona C Effec{onG rl oxygen of an alcetherkr 5 f/aSl.OS -P;?<9'+ Iu q F U'g5 F orygenoraester410 f o, t {[S,Olrp,5 *:7'i E [1 E carbony(c=o)+J r/or F *{:A!=A,A -"1-oFn t r F q!- I Theintusilofthe signal indino*^rrv flrVl&Jl{rSPP'hkfd I lndklate lhe number of signals and theof each siithe following molecules: I F Q"u5 F CHCITCHa -rt3 t c( b Eur ' E Ut $:0 Br-Cq,CHb(CHe)z 2;l:6t E Tle af flte sitelus aboutthe r $frirg What rvobethe splitteachofotoin the rnobcules below? CHs-CHz-Cl q6 E +xpU Wilil-el ub E F-CHrCHrBr q hrpltt cr. b ^nN*I t c &6c t 3 ?'. sh&l*t eytpheJ_u6tct H3C-C-CH-CH3 or.60 t CI-CHrCH2-Cl tn,,"Jq,,\+Egulwta4 ,*i"re d, nol-Jpliwd oW 0. 0( gP,lB,e{ 1S6 ThegenerappearanofaprotoNMR spclfrum. ldentiTMS, upfield, downfield, shiinthspectrum below: 'il*n&,Jd' orphr)d't 6--...- ,aur,ld.lhddeJ' ilshre/drd/ +- rto.s - ExamplesPredthe NMR spectra of the compounds below. J $$torl Wb,zi2fsnes Br Br or sfuItl 'b II w 't' CHz - cHz che.nlcqshr4l",b* z_g Uq I I - - T----- 3 r I i 16-7 I I CHs-CHBrz, Qt6 Qr .b ?^hr$+) bl l Iu E d"'tlt+ n*J'+ 6 *Afl'24 t I r r t : .01 E ' Urarydk coehol E r F b t i r E E F tc) I l+ ;o- 3 1tr t E F Lr; 3. E 69l, ,*:r,, i E T*f-rr *nplel E X*fu+ 2j' t ^fl,! t xThe rtunolo*ko dorr,,rXrtil upkrld I rpftary,nco e{- ehrcl1 lwrlet 4*/eL t t q t ; 6 t E {tw t t $/ t t r q 1ffi Br oA6 I 6 oJ cH:- cH- CHr drult4 s(P+.+ c(64 E "CI"? 2-l Chwcl"re*ke, q ?qprppyl App"annc,tl 8.@0p ] c[,-cll- "I ctla 6 I I 3 2 00( 6 cd q o H"C lt 6:J;2r3 .cH-o-c- cH2cH3 t,lutnelrVrtj,+nplr.." 5 6 a' d 09.t*6JJ^,z+XU,9*z ,t., JE <gE ls"r {+ c v ,/tt , /I lr I ru>*l ---T----- 5 2 1 0 1G9 NMR- AdditionalDetaits 'H \-/ 1. ChemicalShitrs6) .Chemical shifts are measured relative to of absorptotnT M 6 flclrqrr{d SffaflZ/ Silane TetramethyS/ane t"o{w t rfE H-Sr- lu 8116bl I +1,cAflr;cq M "tpl, .Sincecarbois l\afL electronegative than silicon, inTMS areI\*o Skfddld qlqgs'l thanin most other orcompounds.8o 'thgrctql rs uluruys Qtlh.4*Vpkdd .The position the NMspectrums called the che,,\Pral or8 $= EpecLs",ulnr txqur.noy witunitot:ppw) tmportant:e GhemicaShifi doestdependon4he qOr.dfn5 Ae*ooy ,t the prrSl-^t^A], Example:On a 300 MHz NMRspectrometer, theonof benzene absora frequency of rf radiais2181 Hz ';,m:"#:*^;-i"s '/' ff a rMS'what'",Y,"TT'T'"n'::-",.ead, theonor/n un"absorb afrequency tis436 Hzawayfrom y)u-'fffi.6 t t, .,t .?u gq# ; *p{ r'udepe^re+ s{-Me v; fnab,p*q,Unq'WW- W, ' On a 500MHz NMR,a'H NMR signaloccuneat6.75. Howmany Hzdownfield from Tithis? 5. ok= 8t r,r{26rc(x5@i{6,ry ffi, Ona 200 MHz instrumifthe sigis6.756,ow many Hz downfifrom TMSwouldthirepresent? 'J \'/ 9s, CI(s' E <r*h= 6Fg 6 8n*r 16-10 2. Spin-SpilnSplitttng ithe signal. Spin-spin splitting,Ug ,occurs when interacts with the - f+.eld proauuvJ heor/bV protons. ExamBlCHzBTCHBTz a(b h*1t Bi'-'tPr A,tg H, I I A il I 116 ,f l,_ J[ [L 6-)+> v ru thatH"experiencesdepends*o({4e neBh6oreq EPfle paolOrs ExampleCHBT2CH3 16-1 0rb \./ *'^ Jr6 Br\;(\'Hb Bf [lu l+6 I I I ffi I Irt fIJ fJ^, fJl ,[f] t ttt t't 'l.l.tJJ When signsplitloc,curthe distabetweethe individualofasigniscalled the C@e pls/\3 C$ng,Jqd ,o,. 0-m,I,,r, Summaryof$fn-SpinSplitting: 1. chemicauyequivatentprotons @& qWr dO n**Splfff exampss: cl C' t' I I d,^t -r, Ct+r-?Hz Hr t/\ .gqprwiui €q, l',qi{rni [ddno| sp,h,,) dd 4d-spl*J- 2. Thesignalofaprotonthatnas neighboringprotonsiint^itnUJ{rylp{ or n4J 3. Twognoupofg&rsoryIedbeadrdnrlmethesare CodanJ, r C*{frfL, rt nctp,nc,tw},lw*fup 1&13 Determiniftheydrogensshown are homotopic, enardiotopic, diaornotrelated at all. QH w" P"x .arlroloptc .horologo "dtqsloa{opm alar,l .e1pryiqi- -ano 'eryJ, ,asa gpffMln{ "sqpuaffi fiutwleal 4. NllRTimeSeale The NMR time scale is relatively,, .i\bsorptiof lRadiatiisessentiallTns{r,zr*oU.q . But NMRis ,ilor,^r- andany typofmovementor changthatakesplace ^O+thA fastertha^wut Zerpnd willproducanaverageNMRsignal. SoWhatil?? Twoimpodant consequences: 1. Chair-to+hainterconversiofcyctohexafiealscalle"------\:r--- - !to fvAt*t L-------/ \1. \-/ Ane,1a<aK q st4gkl 'HNrun of cyclohexane: at25oC T* at-50oC sk^k # qPade tnh at-70oC e pql6 L p<atlc L k?ds o( goth<s,: '1, at-100oC *f (qucrh^?al "f$rl 16-14 2. NMR ofalcabols .Even trace amounts offal p+t cancatalyze 0"d10; ;lrwg{-^e" on a timescare more rapid than that ofsothathere is U''''l?d,' Protoexchanoe: k-a[o + MS +: A- oi+6 * [,+u+' 6seS{nfie} cH3-cH-cH3 Example:CH3CH2CH2OH t*ru +'tpfsrngle'f .When small amountsDzOare added an alcohol, theol) isexchangedor t/S tl.+*"tu;, e andthe-oHabsorption (dPaqr.#q.s ,M D, Qors gg AoD Jp *J'; This allousto determine whicuMR absorption wdueto hg -0/U B.ofroa 1H .Butwhen the NMR spectruofan alcohisrunidimethysulfoxide,t] M S0 ,protoexchangeis eAr.,plPS *u"n B-lqrUar thanheNMRtime scateso SpPo-Sp9o occurs- * dablei CH3-CH-CT. Example:-H3CH2CH2OH inDMSO- toek] inOtvtSO t***t g| o dr,6tl'*ll+u*i*fuairoldopJ*4r,h, --"I{tpful ' '3c NMR .,-1J y, 1. Mostcarbon atoare " C .only ofnaturaloccunincarbon," "C 13C qkag 2. The numbeofsignalia NMR spectrum represents the n"rk*ad* ,lc"r6o, 3. ln13cNMR,tne gnlgB rulrgn (i.enumber of atoms causing the signal) and are not reported. This simplifies interpretation. 4. The chemical shveryimportant: CI sp' desfil&ld&/ SP5 II C .-C- - sp3c I C*bonyt w,$w 15 ,c=q* c-N "$G- a hu,qty d{s4f€fded C-o CI spc n-f v,iv ?+o Jso n)ao N PP', b 16-15 A compounwith molecularC7H1aOdisplathe followingNMR and3CNMR spectra.posa structure for this compound. CtHrqAr) Crlg,a Lc*01 uni'i-lngqiu"q*foa o"f;/l:rfl, n-J-r-a Stxi-rl 6 k+nA er ,L Pdoas &.^fl ttr,.* clectL-rpi X ct+r-i,tt$t-ouivctlr-et4 J;P+l hpirl- iptet Lry *eli rnul ,nailprd .r. L ,-.jt^' -8 - r,,-.ctt"cp3 "$*B 11 1() pprrl J,z{J %?-- ct,ao! ff "t 16-12 3. ProtonEquivalence PrlncipleProtons in different enviromagnetically and absorb energy at differentWfftnCVq To determinitwo hydragenaremagneticallyivalentornon eguivatereplaee eahydragenwith X. 1. rr Ooa*.lt[iirorqI .?sootr,e resurthen the hydrosens are nq{- {Ytsk d and armasneticany q t'l-Wfuqfiql- Exampte: "fi.-"tfr-"8. cl5c WrCUr_ q,q!) ctlrSllre\ ailr*tuJf ^ U,-rJ*-t 2. lfou gethe same compouregardleofwhichhydrogenoureplace, the hydrarens horahf*r ano6rus eufuq,e/rl Examptecfrr-crlrcH3 cnr-c('",,1 cu'c(,",-x cHd-c('zc,,.h cHic(i"-,t -'Jry"+'pro s\ s\ ql+ vx 3. lfou gedifferent enantiomers, the are enq,nfuof?O and are masneticallyql'&lqlod ExampleCH3-CH2-CH2-CH3 cn;c(2 -cHa cn;c\,-*r. cnr-c\-cu. HH\ j\ b4x XU G) 4. lfou gedifferent diasterthe hydrogeu. df A'lv{rn*oro/rA and are masneticauyna^ q?d$qJ/rll Example: ry..P* HOH ryP' 1t H3c'c'6'He H.c-c;.c;cH' H3C-c'6-cHs n* |. s\ (Rl-akr*.r W\ xF+ LzB,ak] {zqxt


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